CN105567183A - Composite emulsifier for oil-based drilling fluid, and preparation method and application thereof - Google Patents
Composite emulsifier for oil-based drilling fluid, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a composite emulsifier for an oil-based drilling fluid, and a preparation method and application thereof. The main objective of the invention is to overcome the problems of a few varieties, poor emulsification performance and poor temperature resistance of emulsifiers for the oil-based drilling fluid in the prior art. The composite emulsifier for the oil-based drilling fluid in the invention comprises a main emulsifier, which is at least one selected from structures as shown in a formula (I) described in the specification, and a coemulsifier, which is at least one selected from structures as shown in a formula (II) described in the specification, wherein the ratio of main emulsifier to coemulsifier is more than 0 and no more than 1. Thus, the above-mentioned problems are overcome; the composite emulsifier can be used for the oil-based drilling fluid and has good emulsification performance and temperature resistance; and the formed oil-based drilling fluid has good stability and temperature resistance and can meet special demands of well drilling in a high-temperature stratum with strong water sensitivity, large-displacement special well drilling, an offshore horizontal well and the like in oil fields.
Description
Technical field
The present invention relates to a kind of oil base drilling fluid compound emulsifying agent and its preparation method and application.
Background technology
Along with the continuous minimizing of prospective oil and exploitation difficulty, countries in the world increase the input to deep formation Oil And Gas Exploration And Development one after another, develop an urgent demand that new oil reservoir has become the development of current each major oil companies.China's hydrocarbon resources to be verified mainly is distributed in Tarim Basin, Zhunger Basin, Qaidam, tells the basins such as Kazakhstan, Sichuan, 73% of its stock number is imbedded in deep layer, and underground condition complex, therefore deep-well and ultra deep well oil gas drilling and supporting development technique have become the key factor of restriction petrol resources exploitation.Along with the increase of depth of stratum, the formation temperature of deep-well, ultra deep well also can be more and more higher, and can the hot environment on stratum maintain stable performance to drilling fluid and bring great challenge.
Drilling fluid is as the important component part of drilling engineering, and its performance is directly connected to deep-well, the drilling quality of ultra deep well, drilling cost and drilling period.Relative to water-base drilling fluid; oil base drilling fluid has stronger anti-collapse inhibition, oilness and good reservoir protection performance; especially can meet strong retraction and high temperature, ultrahigh-temperature stratum, or need to bore that Large travel range exceptional well and seaborne horizontal well etc. are special turns drilling well needs.Oil base drilling fluid, also known as invert mud, is made up of oil, water, emulsifying agent, fluid loss agent, equilibrium of activation agent, flow pattern regulator etc.Between 5 ~ 30%, (water content is generally called full oil base drilling fluid to normally used invert mud water content within 5%, be not called invert mud), but high temperature resistance reaches the content of water in the invert mud of more than 180 DEG C generally 5 ~ 10%, rarely exceeds 15%.The content of water increases, take bits property, filtration reduction and suspension, rheological all to improve, but thermostability and elctrical stability are all deteriorated, as CN1660958 reports a kind of synthetic base drilling fluid, the mixture that the primary emulsion used is AESA and polyoxyethylene nonylphenol ether, although still have good rheological and emulsion-breaking voltage at 150 DEG C after aging 16 hours, water-content is up to 25%.A kind of high-temperature water-in-oil drilling fluid of patent CN102031095A Shen Qing Publication, although heatproof can to 240 DEG C, it just must can reach effect by the existence of co-emulsifier and calcium oxide.Oil base drilling fluid is because base fluid is based on oil, therefore expensive, cost is high, full oil base drilling fluid is all the more so, as CN101215461 reports a kind of complete-oil synthetic base drilling fluid, the emulsifying agent of use is Long carbon chain fatty acid amide, one or more mixture in Long carbon chain alkyl benzene calcium sulfonate, polyolefin carboxylic acid's ester, although have low toxicity, environmental protection, to advantages such as reservoir damage are little, but its preparation cost is high, limits it and promote the use of.
What provide as oil base drilling fluid emulsifying agent in the market is of less types, and the emulsifying agent kind that report is used for intensified oil reduction is relatively many, as US4485873, US4545912, CN100531884 etc. report polyxyethylated alkylphenol acetate, two tail chain polyoxyethylene sulfonic acid salt, the application of alkyl-fragrant benzyl-polyethenoxy ether negatively charged ion surfactant in intensified oil reduction, but do not relate to its purposes in well-drilling liquid emulgent.Domestic oil base drilling fluid emulsifying agent aspect many dependences external product, and domestic supporting drilling fluid system is also less.
Oil base drilling fluid is owing to being subject to cost, the restriction of environmental requirement develops slower always, the block of application is also less, along with existing oilfield reserve declines day by day, and the exploitation in new exploratory area can run into various bad ground and environment, be badly in need of carrying out meeting the research preparing stability and high efficiency oil base drilling fluid emulsifying agent, few to solve oil base drilling fluid emulsifying agent kind, emulsifying property is poor, not salt tolerant, the not problem of heatproof, the Cost Problems reducing oil base drilling fluid is reached by the ratio improving water in oil base drilling fluid, for the operation of widespread use oil base drilling fluid provides technical support.
In this high-moisture situation just of the present invention, be suitable for compound emulsifying agent preparing stability and high efficiency oil base drilling fluid and preparation method thereof.
Summary of the invention
One of technical problem to be solved by this invention is that in prior art, oil base drilling fluid emulsifying agent kind is few, and the problem of emulsifying property, heat resistance difference, provides a kind of oil base drilling fluid compound emulsifying agent.This oil base drilling fluid compound emulsifying agent has good emulsifying performance and heat resistance, and the oil base drilling fluid containing such oil base drilling fluid compound emulsifying agent can meet the special requirement such as strong retraction in oil field, high-temperature stratum and Large travel range Special Drilling Operation, the drilling well of seaborne horizontal well.
Two of technical problem to be solved by this invention is to provide a kind of preparation method of the oil base drilling fluid compound emulsifying agent corresponding with one of technical solution problem.
Three of technical problem to be solved by this invention is to provide a kind of oil base drilling fluid compound emulsifying agent application in oil base drilling fluid corresponding with one of technical solution problem.
In order to one of solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of oil base drilling fluid compound emulsifying agent, comprises following component:
(1) primary emulsion, is selected from least one in structure shown in formula (I);
(2) co-emulsifier, is selected from least one in polyol-based non-ionic surfactant;
Wherein R
1for containing C
8~ C
30saturated or unsaturated alkyl, R
2for hydrogen or R
3cO, R
3for C
8~ C
30saturated or undersaturated alkyl, x=1 ~ 10, y=1 ~ 40, z=0 ~ 40; In mass, the ratio of described primary emulsion and co-emulsifier meets 0 < co-emulsifier: primary emulsion≤1.
In technique scheme, described R
1and R
3independently be selected from C
11~ C
23saturated or undersaturated alkyl or C
11~ C
23saturated hydrocarbyl and the mixing alkyl of unsaturated alkyl.More preferably R
1and R
3independently be selected from stable hydrocarbon or unsaturated alkyl that carbonatoms is 11,13,15,17,19,21, or the mixing alkyl of the stable hydrocarbon of 11,13,15,17,19,21 and unsaturated hydrocarbons.Preferred x is 2 ~ 6, y be 1 ~ 20, z is 0 ~ 30; Further preferably x be 2 or 3, y be 1 ~ 10; More preferably z is 0 ~ 20.Described polyol-based non-ionic surfactant is selected from polyol and higher aliphatic acid or high-carbon fatty acid ester and reacts the ester formed; It is plural polyvalent alcohol that described polyol refers to hydroxyl quantity, and described polyol is selected from C
2~ C
10polyvalent alcohol or C
2~ C
10polyvalent alcohol acid anhydride, be more preferably ethylene glycol, propylene glycol, glycerol, butyleneglycol, butylene glycol, at least one in trihydroxybutane, butantetraol, sorbyl alcohol, sorbitol anhydride; Described higher aliphatic acid is preferably from C
12~ C
24lipid acid, be more preferably one or more the mixture in lauric acid, tetradecanoic acid, palmitinic acid, physetoleic acid, stearic acid, oleic acid, linolic acid, linolenic acid, one or more the mixture of described high-carbon fatty acid ester preferably in Laurate methyl, Myristicin acid methylester, Uniphat A60, physetoleic acid methyl esters, methyl stearate, Witconol 2301, methyl linoleate, Linolenic acid methylester.
In technique scheme, described polyol-based non-ionic surfactant can by common practise well-known to those skilled in the art, obtained by esterification by described polyol and higher aliphatic acid, or obtained by transesterification reaction by described polyol and high-carbon fatty acid ester.
In technique scheme, described fatty acid methyl ester can derive from various vegetable oil esters well-known to those skilled in the art, such as but do not limit soybean oil, plam oil, ucuhuba oil, vegetable seed wet goods, and artificial biofuel etc. of refining.
In technique scheme, described primary emulsion can two or more mixture further preferably in structure shown in (I).
In technique scheme, described co-emulsifier can preferred two or more mixture in polyol-based non-ionic surfactant further.
In technique scheme, in mass, the ratio of described primary emulsion and co-emulsifier most preferably is co-emulsifier: primary emulsion=1:(1 ~ 10).
In technique scheme, described co-emulsifier can one or more mixture further most preferably in Arlacel-20, Arlacel-60, Arlacel-80, Arlacel-85, ethylene glycol fatty acid ester, di-fatty acid esters.
In technique scheme, the preparation method of described co-emulsifier can be well-known to those skilled in the art any one, can be the one before this in known preparation method disclosed in document.
For solve the problems of the technologies described above two, the technical solution adopted in the present invention is as follows:
A preparation method for oil base drilling fluid emulsifying agent, comprises the following steps:
(a) R
1cONH (CH
2) xNR
2cH
2cH
2the preparation of OH (i.e. fatty acyl hydroxyethyl diamines)
R under basic catalyst exists
1cOOCH
3(i.e. fatty acid methyl ester) and NH
2(CH
2)
xnHCH
2cH
2oH (i.e. hydroxyethyl diamine) reacts 2 ~ 24 hours at the temperature of 80 ~ 220 DEG C, and reaction terminates the methyl alcohol that rear preferred underpressure distillation removes unreacted raw material and generation and obtains described fatty acyl hydroxyethyl diamines.Wherein, the mol ratio of fatty acid methyl ester and hydroxyethyl diamine is preferred 1:0.1 ~ 6.Described catalyst levels preferably accounts for 0.01 ~ 10% of fatty acid methyl ester quality.
(b) R
1cONH (CH
2) xNR
2(CH
2cH
2o)
y-(CH2CHCH
3o)
zthe preparation of H (i.e. fatty acyl group diamines Polyoxyalkylene ethers):
Under basic catalyst exists, the fatty acyl hydroxyethyl diamines synthesized by step (a) and required oxyethane or propylene oxide carry out being obtained by reacting described fat acyl group diamines Polyoxyalkylene ethers.Catalyst levels is preferably 0.5 ~ 6.0% of fatty acyl hydroxyethyl diamines quality;
The preparation of (c) oil base drilling fluid compound emulsifying agent
The described fat acyl group diamines Polyoxyalkylene ethers that described fatty acyl hydroxyethyl diamines step (a) obtained and/or step (b) obtain and described co-emulsifier; mix in described ratio, obtain described oil base drilling fluid compound emulsifying agent.
In technique scheme, temperature of reaction preferable range a) in step is 100 ~ 200 DEG C, is more preferably 120 ~ 180 DEG C; Catalyzer is preferably at least one in alkali metal hydroxide, alkaline earth metal hydroxides, is more preferably potassium hydroxide, sodium hydroxide, more preferably potassium hydroxide, and consumption preferably accounts for 0.5 ~ 5.0% of fatty acid methyl ester class monomer mass; The mol ratio of fatty acid methyl ester and hydroxyethyl diamine is preferably 1 ~ 2:1; Reaction times is preferably 6 ~ 16 hours.
In technique scheme; b) basic catalyst in step is preferably at least one in alkaline earth metal oxide, alkaline earth metal hydroxides; be more preferably at least one in calcium oxide, calcium hydroxide, catalyst levels preferably accounts for 1 ~ 5.0% of fatty acyl hydroxyethyl diamines quality.Temperature of reaction is preferably 85 ~ 180 DEG C, and pressure is preferably less than 0.80MPa gauge pressure.
In technique scheme, described oil base drilling fluid compound emulsifying agent can be that described primary emulsion and co-emulsifier mix and obtain, also both can be dissolved in solvent evenly to obtain, as both being dissolved in 5# white oil, obtain the oil base drilling fluid compound emulsifying agent of paste or solution state.
For solve the problems of the technologies described above three, the technical solution adopted in the present invention is as follows: the application of a kind of oil base drilling fluid emulsifying agent in oil base drilling fluid.
In technique scheme, described application method, those skilled in the art can adopt common practise to be applied according to practical application, such as but do not limit, with the volume mass percent basis accounting for profit of primary emulsion contained by compound emulsifying agent and co-emulsifier, the dosage of compound emulsifying agent for being no less than 0.1%, preferably 0.1 ~ 10%; Described oil base drilling fluid can be full oil base drilling fluid, also can be invert mud; In described application, oil base drilling fluid can add arbitrarily various oil base drilling fluid auxiliary agent well-known to those skilled in the art.
The oil base drilling fluid compound emulsifying agent of fatty acyl group hydroxyethyl diamine prepared by the present invention and/or fatty acyl group diamines Polyoxyalkylene ethers has good resistance to gentle salt resistant character, and there is good solubility and emulsifying stability, and this oil base drilling fluid emulsifying agent has nontoxic, harmless, that biological degradability is good advantage, be suitable for the oil base drilling fluid emulsifying agent being used as high temperature and high salt water-sensitive strata; In addition preparation method of the present invention is simple, and raw material is easy to get, and have good economic feasibility, suitability for industrialized is applied.
Adopt technical scheme of the present invention, be used for oil base drilling fluid with fatty acyl hydroxyethyl diamines and/or fatty acyl group diamines Polyoxyalkylene ethers class tensio-active agent and the compound emulsifying agent of (dehydration) polyhydric alcohol fatty acid ester, it mainly forms and comprises following component: base oil 60 ~ 90 parts, 10 ~ 40 parts, water, compound emulsifying agent 0.5 ~ 5 part (quality in primary emulsion contained by compound emulsifying agent and co-emulsifier); This oil base drilling fluid heatproof is greater than 180 DEG C, API filtration≤1ml, emulsion-breaking voltage >=1200V after high temperature ageing, is that a kind of heat resistance is excellent, filter loss is little, the oil base drilling fluid system of good emulsion stability.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
The synthesis (x=3) of (a) N, N ＇-bis-vegetable oil acid acyl group hydroxyethyl propylene diamine
N-hydroxyethyl propylene diamine 55.3 parts, KOH8.33 part are joined in the reactor being furnished with sealing machine stirring, thermometer, condenser west tube, receiving flask, after stirring 1 hour in 150 DEG C, slowly drip methyl soyate (in mass percentage, methyl soyate comprises following component: tetradecanoic acid formicester 0.557%, palmitinic acid formicester 18.250%, physetoleic acid formicester 1.402%, stearic acid methyl ester 5.495%, oleic acid formicester 30.203%, linolic acid formicester 36.000%, linolenic acid formicester 3.587%, surplus other.) 277.6 parts, dropwise in 1 hour.React 8 hours at 165 DEG C, the methyl alcohol generated in reaction is collected in receiving flask through condenser west tube.Underpressure distillation goes out remaining lower boiling resultant and reaction raw materials, obtains target product N, N ＇-bis-vegetable oil acid acyl group hydroxyethyl propylene diamine.
The synthesis of (b) N, N ＇-bis-vegetable oil acid acyl group hydroxyethyl propylene diamine polyoxyethylene poly-oxygen propylene aether (y=3, z=5)
The N that step (a) is synthesized; N ＇-bis-vegetable oil acid acyl group hydroxyethyl propylene diamine 256 parts, 15.4 parts calcium oxide and calcium hydroxide mixture (calcium oxide and calcium hydroxide weight ratio are 1:1) add in the high-pressure reactor being furnished with condensing works, whipping appts and gas distributor; while lead to nitrogen limit when being heated to 135 DEG C; add 20 parts of water, stirring reaction 1 hour.After removing moisture, be cooled to 80 DEG C, slowly drip the obtained high reactivity of sulfuric acid (20wt%) of catalyst neutralisation theoretical amount, the compound oxidizing calcium alkoxylating catalyst reaction solution system of highly selective, system temperature is heated to 90 DEG C, open vacuum system, dewater 2 hours under a high vacuum, then use nitrogen purging 3 times, system temperature of reaction is adjusted to 160 DEG C and slowly passes into 34.9 parts of oxyethane, control pressure≤0.60MPa.After reacting ethylene oxide is complete; add 114.8 parts of propylene oxide; reaction is continued in 160 DEG C; after reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration; obtain N; N ＇-bis-vegetable oil acid acyl group hydroxyethylethylene diamine Soxylat A 25-7 (y=3, z=5) 343.7 parts, molar yield 84.7%.
The preparation of (c) oil base drilling fluid compound emulsifying agent
In mass fraction; by the N that 10 parts of steps (a) obtain; the N that N ＇-bis-vegetable oil acid acyl group hydroxyethyl propylene diamine, 30 parts of steps (b) obtain; N ＇-bis-vegetable oil acid acyl group hydroxyethylethylene diamine Soxylat A 25-7 (y=3; z=5) and 10 parts of Arlacel-80s; heated and stirred at 90 DEG C, mixes, and obtains oil base drilling fluid compound emulsifying agent.
[embodiment 2]
The preparation (x=3) of (a) N, N ＇-bis-erucic acid acyl group hydroxyethyl propylene diamine
N-hydroxyethyl propylene diamine 47.13 parts, KOH5.6 part are joined in the reactor being furnished with sealing machine stirring, thermometer, condenser west tube, receiving flask, after stirring 1 hour in 150 DEG C, slowly drips methyl erucate 281.3 parts, dropwise in 1 hour.React at 170 DEG C after 10 hours and stop, the methyl alcohol generated in reaction is collected in receiving flask through condenser west tube.Underpressure distillation goes out remaining lower boiling resultant and reaction raw materials, obtains target product N, N ＇-bis-erucic acid acyl group hydroxyethyl propylene diamine.
The synthesis of (b) N, N ＇-bis-erucic acid acyl group hydroxyethyl propylene diamine polyoxyethylene poly-oxygen propylene aether (y=10, z=20)
The N that step (a) is synthesized; N ＇-bis-erucic acid acyl group hydroxyethyl propylene diamine 320 parts, 9.6 parts calcium oxide and calcium hydroxide mixture (calcium oxide and calcium hydroxide weight ratio are 1:1) add in the high-pressure reactor being furnished with condensing works, whipping appts and gas distributor; while lead to nitrogen limit when being heated to 135 DEG C; add 20 parts of water, stirring reaction 1 hour.After removing moisture, be cooled to 80 DEG C, slowly drip the obtained high reactivity of sulfuric acid (20wt%) of catalyst neutralisation theoretical amount, the compound oxidizing calcium alkoxylating catalyst reaction solution system of highly selective, system temperature is heated to 80 DEG C, open vacuum system, dewater 2 hours under a high vacuum, then use nitrogen purging 3 times, system temperature of reaction is adjusted to 180 DEG C and slowly passes into 167.1 parts of oxyethane, control pressure≤0.60MPa.After reacting ethylene oxide is complete; add 489.4 parts of propylene oxide; reaction is continued in 180 DEG C; after reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration; obtain N; N ＇-bis-erucic acid acyl group hydroxyethyl propylene diamine polyoxyethylene poly-oxygen propylene aether (y=10, z=20) 845.7 parts, molar yield 85.6%.
The preparation of (c) oil base drilling fluid compound emulsifying agent
In mass fraction, by the N that 100 parts of steps (b) obtain, N ＇-bis-erucic acid acyl group hydroxyethyl propylene diamine polyoxyethylene poly-oxygen propylene aether (y=10; z=20) and 10 parts of Arlacel-85s; heated and stirred at 85 DEG C, mixes, and obtains oil base drilling fluid compound emulsifying agent.
[embodiment 3]
The synthesis (x=3) of (a) N, N ＇-bis-vegetable oil acid acyl group hydroxyethyl propylene diamine
N-hydroxyethyl propylene diamine 55.3 parts, KOH8.33 part are joined in the reactor being furnished with sealing machine stirring, thermometer, condenser west tube, receiving flask, after stirring 1 hour in 150 DEG C, slowly drip methyl soyate (in mass percentage, methyl soyate comprises following component: tetradecanoic acid formicester 0.557%, palmitinic acid formicester 18.250%, physetoleic acid formicester 1.402%, stearic acid methyl ester 5.495%, oleic acid formicester 30.203%, linolic acid formicester 36.000%, linolenic acid formicester 3.587%, surplus other.) 277.6 parts, dropwise in 1 hour.React 8 hours at 165 DEG C, the methyl alcohol generated in reaction is collected in receiving flask through condenser west tube.Underpressure distillation goes out remaining lower boiling resultant and reaction raw materials, obtains target product N, N ＇-bis-vegetable oil acid acyl group hydroxyethyl propylene diamine.
The synthesis of (b) N, N ＇-bis-vegetable oil acid acyl group hydroxyethyl propylene diamine Soxylat A 25-7 (y=3, z=0)
The N that step (a) is synthesized; N ＇-bis-vegetable oil acid acyl group hydroxyethyl propylene diamine 256 parts, 15.4 parts calcium oxide and calcium hydroxide mixture (calcium oxide and calcium hydroxide weight ratio are 1:1) add in the high-pressure reactor being furnished with condensing works, whipping appts and gas distributor; while lead to nitrogen limit when being heated to 135 DEG C; add 20 parts of water, stirring reaction 1 hour.After removing moisture, be cooled to 80 DEG C, slowly drip the obtained high reactivity of sulfuric acid (20wt%) of catalyst neutralisation theoretical amount, the compound oxidizing calcium alkoxylating catalyst reaction solution system of highly selective, system temperature is heated to 90 DEG C, open vacuum system, dewater 2 hours under a high vacuum, then use nitrogen purging 3 times, system temperature of reaction is adjusted to 160 DEG C and slowly passes into 34.9 parts of oxyethane, control pressure≤0.60MPa.After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain N, N ＇-bis-vegetable oil acid acyl group hydroxyethyl propylene diamine Soxylat A 25-7 (y=3, z=0) 250.8 parts, molar yield 86.2%.
The preparation of (c) oil base drilling fluid compound emulsifying agent
In mass fraction; by the N that 100 parts of steps (b) obtain; N ＇-bis-vegetable oil acid acyl group hydroxyethyl propylene diamine Soxylat A 25-7 (y=3; z=0) and 100 parts of ethylene glycol list soybean oil acid esters (are obtained by soybean oil and ethylene glycol; in mass percentage; soybean oil comprises following component: tetradecanoic acid formicester 0.557%, palmitinic acid formicester 18.250%, physetoleic acid formicester 1.402%, stearic acid methyl ester 5.495%, oleic acid formicester 30.203%, linolic acid formicester 36.000%, linolenic acid formicester 3.587%, surplus other.), heated and stirred at 80 DEG C, mixes, and obtains oil base drilling fluid compound emulsifying agent.
[embodiment 4]
The synthesis (x=2) of (a) N, N ＇-stearic bicine diester base hydroxyethylethylene diamine
N-hydroxyethyl-ethylenediamine 49 parts, KOH2.7 part are joined in the reactor being furnished with sealing machine stirring, thermometer, condenser west tube, receiving flask, after stirring 1 hour in 145 DEG C, slowly drips methyl stearate 270 parts, dropwise in 1 hour.React 12 hours at 165 DEG C, the methyl alcohol generated in reaction is collected in receiving flask through condenser west tube.Underpressure distillation goes out remaining lower boiling resultant and reaction raw materials, obtains target product N, N ＇-stearic bicine diester base hydroxyethylethylene diamine.
The synthesis of (b) N, N ＇-stearic bicine diester base hydroxyethylethylene diamine polyethenoxy ether (y=1, z=10)
203 grams of N; N ＇-stearic bicine diester base hydroxyethylethylene diamine and 185.4 parts of propylene oxide react to obtain N in 150 DEG C under the effect of 7.6 parts of calcium oxide and calcium hydroxide mixture (calcium oxide and calcium hydroxide weight ratio are 1:1); N ＇-stearic bicine diester base dihydroxy ethyl quadrol polyethenoxy ether (y=1; z=10) 348.5 parts, molar yield 87.7%.
The preparation of (c) oil base drilling fluid compound emulsifying agent
In mass fraction; by the N that 60 parts of steps (b) obtain; N ＇-stearic bicine diester base dihydroxy ethyl quadrol polyethenoxy ether (y=1; z=10) and 10 parts of ethylene glycol bisthioglycolate oleic acid esters and 10 parts of ethylene glycol list cocounut oil acid esters; heated and stirred at 85 DEG C; mix, obtain oil base drilling fluid compound emulsifying agent.
[embodiment 5]
A) preparation (x=2, y=1, z=0) of lauroyl hydroxyethylethylene diamine
N-hydroxyethyl-ethylenediamine 17 parts, KOH1.75 part are joined in the reactor being furnished with sealing machine stirring, thermometer, prolong, receiving flask, after stirring 1 hour in 120 DEG C, slowly drips Laurate methyl 35 parts, dropwise in 1 hour.React 6 hours at 155 DEG C, the methyl alcohol generated in reaction is collected in receiving flask through prolong, and then underpressure distillation goes out remaining lower boiling resultant and reaction raw materials, obtains target product lauroyl hydroxyethylethylene diamine 39.7 parts.
The preparation of (b) oil base drilling fluid compound emulsifying agent
In mass fraction, the lauroyl hydroxyethylethylene diamine 50 parts of steps (a) obtained, 5 parts of Arlacel-60s and 5 parts of Arlacel-85s, heated and stirred at 85 DEG C, mixes, and obtains oil base drilling fluid compound emulsifying agent.
[embodiment 6]
The preparation (x=2) of (a) lauroyl hydroxyethylethylene diamine
N-hydroxyethyl-ethylenediamine 17 parts, KOH0.35 part are joined in the reactor being furnished with sealing machine stirring, thermometer, condenser west tube, receiving flask, after stirring 1 hour in 150 DEG C, slowly drips Laurate methyl 70 parts, dropwise in 1 hour.React 16 hours at 180 DEG C, the methyl alcohol generated in reaction is collected in receiving flask through condenser west tube, and underpressure distillation goes out remaining lower boiling resultant and reaction raw materials, obtains target product fatty acyl hydroxyethyl quadrol.
The synthesis of (b) N, N ＇-bis-lauroyl hydroxyethylethylene diamine Soxylat A 25-7 (y=5, z=0)
The N that step (a) is synthesized; N ＇-bis-lauroyl hydroxyethylethylene diamine 70 parts, 3.5 parts of calcium oxide and calcium hydroxide mixture (calcium oxide and calcium hydroxide weight ratio are 1:1) add in the high-pressure reactor being furnished with condensing works, whipping appts and gas distributor; while lead to nitrogen limit when being heated to 135 DEG C; add 20 parts of water, stirring reaction 1 hour.After removing moisture, be cooled to 80 DEG C, slowly drip the obtained high reactivity of sulfuric acid (20wt%) of catalyst neutralisation theoretical amount, the compound oxidizing calcium alkoxylating catalyst reaction solution system of highly selective, system temperature is heated to 90 DEG C, open vacuum system, dewater 2 hours under a high vacuum, then use nitrogen purging 4 times, system temperature of reaction is adjusted to 140 DEG C and slowly passes into 26.4 parts of oxyethane, control pressure≤0.60MPa.After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain N, N ＇-bis-lauroyl hydroxyethylethylene diamine Soxylat A 25-7 (y=5) 83 parts, molar yield 86.2%.
The preparation of (c) oil base drilling fluid compound emulsifying agent
In mass fraction; by the N that 60 parts of steps (b) obtain; N ＇-bis-lauroyl hydroxyethylethylene diamine Soxylat A 25-7 (y=5) and 10 parts of ethylene glycol monolaurates; join in 150 parts of 5# white oils; heated and stirred at 90 DEG C; mix, obtain oil base drilling fluid compound emulsifying agent.
[embodiment 7]
Adopt the oil base drilling fluid compound emulsifying agent that [embodiment 1] obtains, preparation oil base drilling fluid system, the basic recipe of employing is 210mL5# white oil+90mL20wt%CaCl
2humic acids+1% cis-1,4-polybutadiene rubber (the number-average molecular weight 250,000)+1wt/vol%CaO powder of the aqueous solution+3wt/vol% compound emulsifying agent+3wt/vol% organophilic clay (polynite of palmityl trimethyl ammonium chloride modification)+1wt/vol% cetylamine modification.
Specific experiment process is: get 210mL5# white oil, then 3wt/vol% compound emulsifying agent is added, stir, add 3wt/vol% organophilic clay, 1wt/vol% modified humic acid, 1% cis-1,4-polybutadiene rubber and 1wt/vol%CaO powder more successively, continue to stir, finally add 90mL20wt%CaCl
2the aqueous solution, then stir, obtain stable water-in-oil-type drilling fluid system.The rheological parameter of this water-in-oil-type drilling fluid system, emulsion-breaking voltage and API filtration is measured respectively according to " GB/T16782-1997 oil base drilling fluid On-Site Test Procedure ".Wherein rheological parameter measures under adopting the fast rotational viscosimeter of ZNN-D6 type six 50 degrees Celsius of the sensible instrumentation factory in sea, Qingdao, and calculates plastic viscosity (PV), yield value (YP) and ratio of dynamic shear force/yield value to plastic viscosity (YP/PV) according to formula (1), (2) and (3); Emulsion-breaking voltage (ES) measures by the DWY-2 type drilling fluid elctrical stability determinator 50 DEG C of the sensible instrumentation factory in Qingdao, API filtration is measured by the multi-joint filtration device of SD type, and calculates filter loss (FL) according to formula (4).
Formula (1) PV=θ
600-θ
300(mPa.s)
Formula (2) YP=(θ
300-PV)/2 (Pa)
Formula (3) ratio of dynamic shear force/yield value to plastic viscosity=YP/PV
Formula (4) FL=(FL
30min﹣ FL
7.5min) × 2 (mL)
The above-mentioned water-in-oil-type drilling fluid prepared is put into XGRL-4 type high temp roller process furnace, 180 DEG C of high temperature ageing 16h, measure the rheological parameter of this water-in-oil-type drilling fluid system, emulsion-breaking voltage and API filtration respectively, instrument and process are with before aging, and result is as shown in table 1.
[embodiment 8]
Adopt the oil base drilling fluid compound emulsifying agent that [embodiment 5] obtains, the basic recipe of employing is 270mL5# white oil+30mL20wt%CaCl
2humic acids+1wt/vol% ethylene-propylene rubber(EPR) (the number-average molecular weight 150,000)+1wt/vol%CaO powder of the aqueous solution+2wt/vol% compound emulsifying agent+3wt/vol% organophilic clay (organophilic clay of cetyl trimethylammonium bromide modification)+1wt/vol% cetylamine modification.With [embodiment 7] specific experiment process, measure the rheological parameter of these aging front and back of water-in-oil-type drilling fluid system, emulsion-breaking voltage and API filtration respectively, test result is as shown in table 1.
[comparative example 1]
With [embodiment 7], difference is with 3wt/vol% Arlacel-80 (Span-80) alternative composite emulsifying agent, and all the other are identical, and determine the rheological parameter of water-in-oil-type drilling fluid system, emulsion-breaking voltage and API filtration, result is as shown in table 2.Contrast table 1 data can be found out, the system yield value that Span-80 is formed, emulsion-breaking voltage are all lower, and filter loss is larger.
[comparative example 2]
With [embodiment 7]; difference is with N; N ＇-bis-vegetable oil acid acyl group propylene diamine (x=3; y=0; z=0) be 3:1 be that emulsifying agent dosage 3wt/vol% substitutes compound emulsifying agent of the present invention with Arlacel-80 quality proportioning; all the other are identical, and determine the rheological parameter of water-in-oil-type drilling fluid system, emulsion-breaking voltage and API filtration, result is as shown in table 2.Contrast table 1 data can be found out, the system that N, N ＇-bis-vegetable oil acid acyl group propylene diamine is formed, and aging front and back rheological property is poor, all exceeds measurement range, and the system that emulsion-breaking voltage is also formed than emulsifying agent of the present invention is low.
[comparative example 3]
With [embodiment 7]; difference is with N; N ＇-bis-vegetable oil acid acyl group propylene diamine polyethenoxy ether (x=3; y=0; z=3) be 3:1 be that emulsifying agent dosage 3wt/vol% substitutes compound emulsifying agent of the present invention with Arlacel-80 quality proportioning; all the other are identical, and determine the rheological parameter of water-in-oil-type drilling fluid system, emulsion-breaking voltage and API filtration, result is as shown in table 2.Contrast table 1 data can be found out, the system that N, N ＇-bis-vegetable oil acid acyl group propylene diamine polyethenoxy ether (x=3, y=0, z=3) is formed, and system yield value, the emulsion-breaking voltage of formation are all lower, and filter loss is larger.
[comparative example 4]
With [embodiment 7]; difference is with N; N ＇-bis-vegetable oil acid acyl group propylene diamine polyethenoxy ether (x=3; y=0; z=5) be 3:1 be that emulsifying agent dosage 3wt/vol% substitutes compound emulsifying agent of the present invention with Arlacel-80 quality proportioning; all the other are identical, and determine the rheological parameter of water-in-oil-type drilling fluid system, emulsion-breaking voltage and API filtration, result is as shown in table 2.Contrast table 1 data can be found out, the system that N, N ＇-bis-vegetable oil acid acyl group propylene diamine polyethenoxy ether (x=3, y=0, z=5) is formed, and system yield value, the emulsion-breaking voltage of formation are all lower, and filter loss is larger.
[comparative example 5]
With [embodiment 7], difference is 3:1 with INVERMUL emulsifying agent (production of HalliburtonBaroid company) and Arlacel-80 quality proportioning is that emulsifying agent dosage 3wt/vol% substitutes compound emulsifying agent of the present invention, all the other are identical, determine the rheological parameter of water-in-oil-type drilling fluid system, emulsion-breaking voltage and API filtration, result is as shown in table 2.Contrast table 1 data can be found out, the system that INVERMUL is formed, and aging front and back rheological property is poor, all exceeds measurement range, and the system that emulsion-breaking voltage is also formed than emulsifying agent of the present invention is low.
[comparative example 6]
With [embodiment 7]; difference is with the N obtained in embodiment 1; N ＇-bis-vegetable oil acid acyl group hydroxyethyl propylene diamine and N; N ＇-bis-vegetable oil acid acyl group hydroxyethylethylene diamine Soxylat A 25-7 (y=3; z=5) quality proportioning is 3:1 is emulsifying agent dosage 3wt/vol% alternative composite emulsifying agent; all the other are identical, and determine the rheological parameter of water-in-oil-type drilling fluid system, emulsion-breaking voltage and API filtration, result is as shown in table 2.
[comparative example 7]
With [embodiment 7]; difference is with the N obtained in 3wt/vol% embodiment 1, N ＇-bis-vegetable oil acid acyl group hydroxyethyl propylene diamine alternative composite emulsifying agent, and all the other are identical; determine the rheological parameter of water-in-oil-type drilling fluid system, emulsion-breaking voltage and API filtration, result is as shown in table 2.
[comparative example 8]
With [embodiment 7]; difference is with the N obtained in 3wt/vol% embodiment 1; N ＇-bis-vegetable oil acid acyl group hydroxyethylethylene diamine Soxylat A 25-7 (y=3; z=5) alternative composite emulsifying agent; all the other are identical; determine the rheological parameter of water-in-oil-type drilling fluid system, emulsion-breaking voltage and API filtration, result is as shown in table 2.
Comparative example 7 and comparative example 1, comparative example 6 ~ 8 can be found out, the compound emulsifying agent effect in embodiment 7 is best.
[comparative example 9]
With [embodiment 8]; difference with obtain in embodiment 5 with lauroyl hydroxyethylethylene diamine and Arlacel-60 by quality proportioning 5:1 for emulsifying agent dosage 2wt/vol% substitutes compound emulsifying agent of the present invention; all the other are identical; determine the rheological parameter of water-in-oil-type drilling fluid system, emulsion-breaking voltage and API filtration, result is as shown in table 2.
[comparative example 10]
With [embodiment 8]; difference with obtain in 2wt/vol% embodiment 5 with lauroyl hydroxyethylethylene diamine and Arlacel-85 by quality proportioning 5:1 for emulsifying agent substitutes compound emulsifying agent of the present invention; all the other are identical; determine the rheological parameter of water-in-oil-type drilling fluid system, emulsion-breaking voltage and API filtration, result is as shown in table 2.
Table 1
Table 2
Claims (10)
1. an oil base drilling fluid compound emulsifying agent, comprises following component:
(1) primary emulsion, is selected from least one in structure shown in formula (I);
(2) co-emulsifier, is selected from the one in polyol-based non-ionic surfactant;
Wherein R
1for containing C
8~ C
30saturated or unsaturated alkyl, R
2for hydrogen or R
3cO, R
3for C
8~ C
30saturated or undersaturated alkyl, x=1 ~ 10, y=1 ~ 40, z=0 ~ 40; In mass, the ratio of described primary emulsion and co-emulsifier meets 0 < co-emulsifier: primary emulsion≤1.
2. oil base drilling fluid compound emulsifying agent according to claim 1, is characterized in that described R
1and R
3independently be selected from C
11~ C
23saturated or undersaturated alkyl, or C
11~ C
23saturated hydrocarbyl and the mixing alkyl of unsaturated alkyl.
3. oil base drilling fluid compound emulsifying agent according to claim 1, is characterized in that described polyol-based non-ionic surfactant is selected from polyol and higher aliphatic acid or high-carbon fatty acid ester and reacts the ester formed.
4. oil base drilling fluid compound emulsifying agent according to claim 3, is characterized in that described polyol is selected from C
2~ C
10polyvalent alcohol or C
2~ C
10polyvalent alcohol acid anhydride, described higher aliphatic acid is selected from C
12~ C
24lipid acid, high-carbon fatty acid ester is selected from C
12~ C
24fatty acid methyl ester.
5. oil base drilling fluid compound emulsifying agent according to claim 1, is characterized in that x=2 ~ 6, y=1 ~ 20, z=0 ~ 30.
6. oil base drilling fluid compound emulsifying agent according to claim 5, it is characterized in that x be 2 or 3, y be 1 ~ 10, z=0 ~ 20.
7. a preparation method for the arbitrary described oil base drilling fluid compound emulsifying agent of claim 1 ~ 6, comprises the following steps:
(a) R
1cONH (CH
2) xNR
2cH
2cH
2the preparation of OH (i.e. fatty acyl hydroxyethyl diamines)
R under basic catalyst exists
1cOOCH
3(i.e. fatty acid methyl ester) and NH
2(CH
2)
xnHCH
2cH
2oH (i.e. hydroxyethyl diamine) reacts 2 ~ 24 hours at the temperature of 80 ~ 220 DEG C, and reaction terminates the methyl alcohol that rear preferred underpressure distillation removes unreacted raw material and generation and obtains described fatty acyl hydroxyethyl diamines; Wherein, the mol ratio of fatty acid methyl ester and hydroxyethyl diamine is 1:0.1 ~ 6;
(b) R
1cONH (CH
2) xNR
2(CH
2cH
2o)
y-(CH2CHCH
3o)
zthe preparation of H (i.e. fatty acyl group diamines Polyoxyalkylene ethers):
Under basic catalyst exists, the fatty acyl hydroxyethyl diamines synthesized by step (a) and required oxyethane or propylene oxide carry out being obtained by reacting described fat acyl group diamines Polyoxyalkylene ethers;
The preparation of (c) oil base drilling fluid compound emulsifying agent
The described fat acyl group diamines Polyoxyalkylene ethers that described fatty acyl hydroxyethyl diamines step (a) obtained and/or step (b) obtain and described co-emulsifier; mix in described ratio, obtain described oil base drilling fluid compound emulsifying agent.
8. the preparation method of oil base drilling fluid compound emulsifying agent according to claim 7, is characterized in that the basic catalyst described in step (a) is at least one in alkali metal hydroxide, alkaline earth metal hydroxides.
9. the preparation method of oil base drilling fluid compound emulsifying agent according to claim 7, is characterized in that the basic catalyst described in step (b) is at least one in alkaline earth metal oxide, alkaline earth metal hydroxides.
10. the arbitrary described application of oil base drilling fluid compound emulsifying agent in oil base drilling fluid of claim 1 ~ 6.
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|---|---|---|---|---|
| CN102027092A (en) * | 2008-05-15 | 2011-04-20 | 阿克佐诺贝尔股份有限公司 | Polyamide emulsifier based on polyamines and fatty acid/carboxylic acid for oil based drilling fluid applications |
| CN102093296A (en) * | 2010-11-30 | 2011-06-15 | 广州星业科技股份有限公司 | Synthesis method of imidazoline compound |
| CN103540297A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Composite oil-based emulsifier containing fatty alcohol polyoxyethylene polypropylene oxide ether carboxylate and preparation method thereof |
| CN103897678A (en) * | 2012-12-27 | 2014-07-02 | 中国石油化工股份有限公司 | Water-in-oil drilling fluid and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102027092A (en) * | 2008-05-15 | 2011-04-20 | 阿克佐诺贝尔股份有限公司 | Polyamide emulsifier based on polyamines and fatty acid/carboxylic acid for oil based drilling fluid applications |
| CN102093296A (en) * | 2010-11-30 | 2011-06-15 | 广州星业科技股份有限公司 | Synthesis method of imidazoline compound |
| CN103540297A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Composite oil-based emulsifier containing fatty alcohol polyoxyethylene polypropylene oxide ether carboxylate and preparation method thereof |
| CN103897678A (en) * | 2012-12-27 | 2014-07-02 | 中国石油化工股份有限公司 | Water-in-oil drilling fluid and preparation method thereof |
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